skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: On the composition of bimetallic near-surface alloys in the presence of oxygen and carbon monoxide

Abstract

Periodic, self-consistent density functional theory calculations (GGA-PW91) are used to examine surface segregation in close-packed bimetallic Pt-overlayer alloy surfaces (Pt*/M, M = Au, Ag, Cu, Pd, Ir, Rh, Os, Ru, and Re) in different environments. In particular, we find that the thermodynamically stable surface termination in these Pt*/M alloys can be inverted from Pt-terminated in vacuum to M-terminated under exposure to oxygen (for an M that is more oxophillic than Pt). Interestingly, in many of these alloys, Pt is not driven into the bulk, rather it remains in the first subsurface layer where it enhances oxygen binding through a ligand interaction with the surface metal atoms. On the other hand, exposure to CO provides a much milder driving force for the surface composition inversion. To quantify segregation under catalytically relevant conditions, we constructed approximate phase diagrams for the PtRu systemas a function of O2 and CO chemical potential (temperature, pressure). Lastly, the results show that the surface termination inverts with many orders of magnitude higher CO pressure than with O2.

Authors:
 [1];  [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
EMSL, a National scientific user facility at Pacific Northwest National Laboratory (PNNL); the Center for Nanoscale Materials at Argonne National Laboratory (ANL); and the National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1405322
Grant/Contract Number:  
FG02-05ER15731
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Communications
Additional Journal Information:
Journal Volume: 52; Journal Issue: C; Journal ID: ISSN 1566-7367
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Platinum alloys; Surface segregation; Density functional theory; Catalysis; Oxygen; CO

Citation Formats

Herron, Jeffrey A., and Mavrikakis, Manos. On the composition of bimetallic near-surface alloys in the presence of oxygen and carbon monoxide. United States: N. p., 2013. Web. doi:10.1016/j.catcom.2013.10.021.
Herron, Jeffrey A., & Mavrikakis, Manos. On the composition of bimetallic near-surface alloys in the presence of oxygen and carbon monoxide. United States. doi:10.1016/j.catcom.2013.10.021.
Herron, Jeffrey A., and Mavrikakis, Manos. Fri . "On the composition of bimetallic near-surface alloys in the presence of oxygen and carbon monoxide". United States. doi:10.1016/j.catcom.2013.10.021. https://www.osti.gov/servlets/purl/1405322.
@article{osti_1405322,
title = {On the composition of bimetallic near-surface alloys in the presence of oxygen and carbon monoxide},
author = {Herron, Jeffrey A. and Mavrikakis, Manos},
abstractNote = {Periodic, self-consistent density functional theory calculations (GGA-PW91) are used to examine surface segregation in close-packed bimetallic Pt-overlayer alloy surfaces (Pt*/M, M = Au, Ag, Cu, Pd, Ir, Rh, Os, Ru, and Re) in different environments. In particular, we find that the thermodynamically stable surface termination in these Pt*/M alloys can be inverted from Pt-terminated in vacuum to M-terminated under exposure to oxygen (for an M that is more oxophillic than Pt). Interestingly, in many of these alloys, Pt is not driven into the bulk, rather it remains in the first subsurface layer where it enhances oxygen binding through a ligand interaction with the surface metal atoms. On the other hand, exposure to CO provides a much milder driving force for the surface composition inversion. To quantify segregation under catalytically relevant conditions, we constructed approximate phase diagrams for the PtRu systemas a function of O2 and CO chemical potential (temperature, pressure). Lastly, the results show that the surface termination inverts with many orders of magnitude higher CO pressure than with O2.},
doi = {10.1016/j.catcom.2013.10.021},
journal = {Catalysis Communications},
number = C,
volume = 52,
place = {United States},
year = {2013},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 12 works
Citation information provided by
Web of Science

Save / Share:

Works referencing / citing this record:

Alloy-composition-dependent oxygen reduction reaction activity and electrochemical stability of Pt-based bimetallic systems: a model electrocatalyst study of Pt/Pt x Ni 100−x (111)
journal, January 2018

  • Todoroki, Naoto; Kawamura, Ryutaro; Asano, Masato
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 17
  • DOI: 10.1039/c8cp01217b

Mechanistic study of dry reforming of ethane by CO 2 on a bimetallic PtNi(111) model surface
journal, January 2018

  • Kattel, Shyam; Chen, Jingguang G.; Liu, Ping
  • Catalysis Science & Technology, Vol. 8, Issue 15
  • DOI: 10.1039/c8cy00880a

Probing catalytic surfaces by correlative scanning photoemission electron microscopy and atom probe tomography
journal, January 2020

  • Schweinar, Kevin; Nicholls, Rachel L.; Rajamathi, Catherine R.
  • Journal of Materials Chemistry A, Vol. 8, Issue 1
  • DOI: 10.1039/c9ta10818a

Ir-Ni Bimetallic OER Catalysts Prepared by Controlled Ni Electrodeposition on Irpoly and Ir(111)
journal, December 2018